Fluorinated Thermoplastic Polyurethanes

Patent Title: SHOE UPPERS & CASE FOR PORTABLE DEVICES

 Number/Link: WO2018/007359  WO2018007360

Applicant/Assignee:  Solvay

Publication date:  11 January 2018

Gist”:  F-TPUs are prepared by incorporating perfluoro diols

Why it is interesting: The current inventions are about fluorinated TPU and its applications. The F-TPUs are prepared by replacing part of the polyol with hydroxyl-ended fluorinated polyethers. In the examples fluorinated polyether diols are used in different ratios to conventional polyester-, PTMEG-, CAPA- and polycarbonate diols and reacted with MDI or HDI and BDO or HDO as chain extenders. The F-TPUs can be used as uppers for footwear and as cases for smartphones and are said to have improved stain resistance and – surprisingly- a soft feel to the touch.

case

F-TPU smartphone case

 

Polyamide Polymer Polyols

Patent Title: POLYAMIDE DISPERSION IN POLYOL AND PREPARATION THEREOF

 Number/Link: WO2017/216209

Applicant/Assignee:  BASF

Publication date: 21 December 2017

Gist”: Polyamide particles from polyether diamine and adipic acid are dispersed in polyol

Why it is interesting: Conventional polymer polyols contain either SAN-, polyurethane- or polyurea particles (see e.g. here).  According to this invention, polymer polyol dispersions can also be prepared by reacting a diamine, containing at least 50 wt% of a linear polyether having two terminal primary amine groups with a dicarboxylic acid (e.g. adipic acid) in a polyether polyol.  The reaction results in a dispersion of polyamide particles in the polyether polyol, stabilized by the polyether diamine. The polymer polyols are useful for flexible foam production and are said to show an improved hydrolysis resistance.

adipicacid

Adipic acid

Natural Oil Polyols using Self-Metathesis

Patent Title: POLYOLS FORMED FROM SELF-METATHESIZED NATURAL OILS AND THEIR USE IN MAKING POLYURETHANE FOAMS

 Number/Link: US2017/0291983

Applicant/Assignee:  Trent Univ.

Publication date: 12 october 2017

Gist”: NOPs from self-metathesized soy oils

Why it is interesting: The use of metathesis chemistry to modify natural oils before converting them to polyols has been discussed before in this blog:  see e.g. US2015/0337073, to the same applicant, which relates to cross-metathesis of natural oils using (e.g.) 1-butene. The current case is about self-metathesis of unsaturated natural oils, resulting in ‘metathesis oligomers’ which are then (partially) epoxidated and hydroxylated to prepare the polyols. In the examples soybean oil is turned into polyols with OH values between about 100 and 250, which are used to make flexible foams with densities of more than 150 kg/m³.

Oligomer from self-metathesis of unsaturated triglycerid


Monodisperse Polymer Polyol

Patent Title: PROCESS MAKING POLYMER POLYOL HAVING MONODISPERSE DISPERSED POLYMER PARTICLES

 Number/Link: WO2017/172417

Applicant/Assignee:  Dow

Publication date: 5 october 2017

Gist”: Polymer polyol with a “monodisperse” particle size distribution is prepared by using a specific seeding dispersion

Why it is interesting: It is well known that the use of polymer polyols in flexible polyurethane foam formulations can result in improved airflow and load bearing properties. For optimal results the average particle size of the dispersed polymer needs to be similar to the cell wall thickness. According to this invention a SAN polymer polyol with a controlled and narrow particle size distribution can be prepared by using a seed dispersion which consists of an unsaturated macromer which, together with SAN particles of a particle size between 50 and 500 nm, is dispersed in a base polyol. The macromer is a PO/EO polyether with a (pref.) mole weight of 11000 to 14000 Da and having 4-5 OH groups and 1-2 reactive double bonds. The polymer polyol is prepared by dispersing the seed dispersion in the base polyol together with styrene, acrylonitrile and a solvent (e.g. isopropanol). After polymerization of the monomers the solvent is removed, resulting in a polymer polyol with at least 30% solids, average particle size of 1-3 μm and a size span of 1.25. In the examples the macromer is prepared by capping 1-2 OH groups of a 6-functional 90/10 PO/EO polyol with 3,3-isoprenyl-α,α-dimethylbenzylisocyanate.

3,3-isoprenyl-α,α-dimethylbenzylisocyanate

 

 

Rigid Thermoplastic Polyurethanes

Patent Title: ISOCYANATE-MODIFIED RIGID THERMOPLASTIC POLYMER COMPOSITIONS

 Number/Link: WO2017/146948  WO2017/146949

Applicant/Assignee: Eastman Chemical

Publication date: 31 august 2017

Gist”: A “rigid”, high Tg polyester diol is extended with 4,4′ MDI

Why it is interesting: Rigid, high modulus TPUs have been known for a long time – see e.g. Upjohn’s classic patent on ‘Isoplast’ from 1981. These materials are high hardblock TPUs made from diisocyanates, chain extenders with only a small amount of high molecular weight diol as an impact modifier. According to the current invention however, rigid TPUs can be made using less than 40% (w/w) of diisocyanate, a high Tg polyester diol and optionally some chain extender.  The polyester is prepared from ‘rigid’ diols like isosorbide or 1,4-cyclohexanedimethanol together with a ‘rigid’ diacid like terephthalic acid, such that the diol has a MW of more than 400 Dalton and a Tg of more than 40°C. The diisocyanate is pref. 4,4-MDI. The rigid TPUs have a Tg of more than 145°C and a tensile modulus of 1 GPa or higher. They are said to be less moisture sensitive than conventional rigid TPUs.

1,4-cyclohexanedimethanol